EP0001710B1

EP0001710B1 - A heat resistant sealing composition, a method of making this composition, a method of making a ceramic-cermet seal in electric discharge devices and the device thus obtained

Info

Publication number: EP0001710B1
Application number: EP19780300517
Authority: EP
Inventors: Peter Hing; Ehsan Ullah Khan
Original assignee: Thorn EMI PLC
Current assignee: Thorn EMI PLC
Priority date: 1977-10-20
Filing date: 1978-10-18
Publication date: 1982-05-12
Also published as: JPS6236992B2; DE2861823D1; WO1979000220A1; CA1110279A; JPS54500088A; EP0001710A1

Description

The present invention relates to sealing materials suitable for making heat-resistant, and usually hermetic, seals between components of electrical discharge devices.
It has been known for a number of years, as revealed in US-A 3,588,573 and DE-A 2,307,191, that the current sealing material for high pressure sodium lamps based on a modified calcium magnesium aluminate composition with barium oxide and a small amount of boric oxide is chemically inadequate in the presence of reactive metal halide vapours at around 800°C. In US-A 3,588,573 a family of high temperature metal halide resistant sealing compounds using alumina and rare-earth oxides with high melting points ranging from 1720°C to 1800°C is disclosed. The use of such high temperatures for sealing the end of the arc tubes, particularly in the case of short tubes, presents considerable technical problems. For instance, it can easily cause volatilisation of the metal halide species in the final lamp processing.
DE-A 2,307,191 discloses the use of some sealing compounds in the Al₂O₃―SiO₂―MnO system, which are claimed to be metal halide resistant. The silica in the sealing compound is likely to interact with certain metal halides, such as scandium iodide, commonly used in conventional metal halide lamps with a silica envelope. The reaction between scandium iodide and silica is a well-known factor limiting the colour rendition and efficiency of these lamps. The disclosure by Matsushita in A.A. 47-34066 of an unspecified metal halide resistant sealing material of the Al₂O₃―SiO2_―B₂O₃―BeO type is also suspect because of the presence of silica. It is also likely to be objectionable in the lighting industry because of the presence of beryllia, which is a highly toxic material. FR-A 2360535 discloses a sealing material comprising at least two of the oxides A1₂0₃,sio₂ and B₂0₃ together with at least one of the oxides La₂0₃ and Y₂0₃.
We now provide in accordance with this invention sealing compositions for use in electrical discharge devices comprising by weight from 60 to 95% of a rare earth oxide, from 5 to 40% of boric oxide, an amount of up to 5% of phosphorus pentoxide, and an amount of up to 5% of one or of each of aluminium oxide and magnesium oxide. Our sealing compositions are useful in the construction of seals in ceramic discharge lamps, more especially between sintered ceramic oxides such as alumina, and cermet materials such as those disclosed in our Application GB-A 1571084 for example alumina-tungsten and alumina-molybdenum cermets. Seals made with these compositions are, moreover, found to retain their hermetic properties and integrity without any sign of chemical attack after 100 hours at 900°C in reactive metal halide vapours such as mercuric chloride, mercury iodide, sodium chloride, tin chloride, scandium iodide, sodium iodide or cesium iodide.
Although the preferred rare earth oxide is lanthanum oxide, other rare earth oxides, such as Sm, Nd, Sc, Y, Yb, Dy or Ce oxides, or mixed rare earth oxides, can also be used.
Also in accordance with this invention it has further been found that hermetic seals between dense alumina components, cermet components or alumina and cermet components can be prepared by using the composition defined above in vacuum or inert atmospheres between 1100°C and 1650°C.
In particular, compositions around the eutectic compositions of the rare earth and boric oxides, for example at 89.68% by weight lanthanum oxide and 10.32% by weight of boric oxide, have been found to seal translucent alumina arc tubes to alumina-tungsten cermets at 1350°C. The sealing material at the join between the sintered alumina and cermet components consists mainly of the two major crystalline phases: in the case of lanthanum oxide 3La₂o_3'B₂₀₃ and La₂o₃.B₂0₃. These crystalline phases precipitated from the melt during cooling are quite coarse, typically several hundred microns in diameter.
The assembly of large crystalline phases, although not obviously detrimental to the construction of hermetic seals, lowers the strength of the seal and is liable to initiate cracks during thermal cycling. As stated above, we thus add a small amount (up to 5%) of phosphorus pentoxide, together with up to 5% of one or of each of aluminium oxide and magnesium oxide. This results in the formation of aluminium phosphate and/or magnesium phosphate and reduces the size of the precipitated phases by at least an order of magnitude, typically to the order of 3 to 5 microns in diameter. The morphology of the precipitated phases is also drastically altered from large octahedral crystalline phases to needle-like platelets. Although the exact mechanisms responsible for the microstructual changes are not well understood, the included additive such as phosphorus pentoxide, aluminium oxide and magnesium oxide, preferably up to a total of about 3% by weight, drastically increase the rate of crystal nucleation during solidification and subsequently increase the number of crystalline phase per unit volume. Thus a preferred composition is about 88% by weight lanthanum oxide, 10.50% by weight boric oxide, 0.5% by weight aluminium oxide, 0.5% by weight magnesium oxide and 0.5% by weight phosphorus pentoxide.
A preferred method of preparing the sealing compound of this invention consists of mixing the appropriate amount of rare earth oxide, obtained through a soluble salt such as the nitrate, sulphate or oxalate, with boric oxide. The additives can also be added as oxides or through a soluble salt or their respective phosphates. The mixture is then fused at 200°C for 2 hours to homogenize the materials, calcined at up to 1200°C for 7 hours, in air or inert atmosphere, crushed and sieved through a 250 micron aperture mesh. The fusion temperature and fusing time are not particularly critical as this technique simply helps to homogenize all the constituents. However, a preferred calcining temperature in air or inert atmosphere is 900°C for the production of fine mixed oxide powders with good flow, pressing and ejection characteristics, thus permitting the formation of elements such as discs, thin rings or washers. The fusion and calcination must be carried out in high purity alumina or platinum crucibles to avoid picking up undesirable impurities which could adversely affect the sealing behaviour.
The frit can be applied in the form of a slurry, using an organic liquid such as methyl or ethyl alcohol; the frit slurry or a preformed ring or disc can then be prefixed or premelted on the ceramic or cermet component prior to the final sealing operation. Premelted frit on the ceramic components offers additional advantages as it removes trapped air, moisture and other residual volatile species which could interfere with the final ceramic lamp processing.
The lanthanum oxide compositions set forth in the Table possess excellent wettability. They represent preferred percentage ranges of the individual constituents, but not the limits of useful compositions.
Sealing the components between 1325°C and 1500°C with a tantalum heating element or by radio frequency heating permits the formation of a good fillet between the alumina components and the cermet components or between the alumina to cermet components without producing unnecessary flow of the sealing materials, for instance, along the length of the alumina arc tube. The alumina arc tube may be a sintered alumina or artificial sapphire tube.
The heating rate should preferably not exceed 700°C per minute to avoid entrapment of air in the melted sealing materials. A suitable heating rate is 400°C per minute as this minimises the formation of air bubbles. Holding the temperature for 2 minutes, moreover, helps the sealing materials to wet the alumina arc tube and the cermet components. The sealing materials are suitable for joining components irrespective of whether the surfaces are machined, polished or in the as-sintered condition.
Another important factor in the construction of a hermetic seal between alumina and cermet materials is the rate of cooling of the melt, a preferred cooling rate being 40°C per minute for 5 minutes after melting and holding the melt for 2 minutes, followed by a cooling rate not exceeding 80°C per minute for another 15 minutes. The cooling rate allows the additives to act synergetically in the production of small interlocking crystalline phases, which confers improved strength on the seal, thus enabling it to withstand thermal cycling as is necessary for lamp operation.
It has further been found that by increasing the amount of boric oxide in the La₂0,.B₂0₁ system beyond near eutectic proportions, hermetic seals can be effected at temperatures as low as 1100°C. The upper limit of sealing temperatures is as high as 1600°C. Table II below shows the compositions and the minimum temperatures at which hermetic seals have been obtained between alumina envelopes and cermet caps.
Apart from the addition of small amounts of phosphorus pentoxide, alumina and magnesia, other rare-earth oxides, for example those of yttrium, ytterbium, samarium, dysprosium and cerium, can be additionally incorporated in the La₂O₃.B₂O₃ system to enhance the properties of the seals. The total amount of these minor oxides should preferably not exceed 5% by weight. It is desirable, but not essential, to include these minor additions to effect hermetic seals. Examples of compositions with such additions which have been successfully used for obtaining hermetic seals are shown in the following Table III.
The most successful compositions of this kind fall in the range of proportions by weight: 60 to 95% lanthanum oxide, 5 to 40% boric oxide, 0 to 5% phosphorus pentoxide, 0 to 5% aluminium oxide, 0 to 5% magnesium oxide, 0 to 5% other rare earth oxide, such as dysprosium oxide, cerium oxide, ytterbium oxide or samarium oxide.
As already mentioned, sealing compositions can be based on rare earth oxides other than lanthanum oxide, such as samarium oxide and neodymium oxide. These sealing compounds in, for example, the Sm₂O₃.B₂O₃ and Nd₂O₃.B₂O₃ systems are similar to those in the La₂0₃.B₂0₃ system. Table IV below shows some useful sealing compositions of this kind.
Seals described herein as hermetic will usually be impervious to helium. Such seals are achieved by the preferred compositions and methods here described but it will be appreciated that such a degree of hermeticity may not always be required
In the accompanying drawings:

Fig. 1 is a diagram illustrating a typical sealing sequence;
Fig. 2 shows one example of a lamp seal constructed with the help of the materials of this invention; and _ _ _
Fig. 3 shows a further example of a constructed seal.

In Fig. 1, in which temperature is plotted against time, one example is given of a heating and cooling sequence suitable for sealing an alumina component to a cermet component. After initial heating to 1400°C in the region A, the seal is held at this temperature (region B) and subsequently allowed to cool slowly. The first stage of cooling C is more gradual than the second stage D.
Constructed seals are shown by way of example only in Figs 2 and 3. These seals have withstood metal halide vapours such as mercuric chloride, mercuric iodide, sodium chloride, tin chloride, scandium iodide, sodium iodide or cesium iodide at 900°C for at least 100 hours without any visible sign of chemical reaction. the seals remain hermetic after exposure to these active metal halides used in a variety of metal halide lamps. In the lamp of Fig. 2, a cermet cap 11 carrying the electrode 15 is placed on a frit ring 12 composed of the sealing material of this invention at the end of an alumina arc tube 13 with a monolithic alumina plug 14. Fig. 3 shows a completely sealed unit ready for incorporation into a ceramic discharge lamp. The reference numerals have the same significance as in Fig. 2..
The sealing materials of this invention can be used in a variety of ways for the construction of ceramic discharge lamps containing sodium and/or metal halide vapours in alumina arc tubes. For instance, they can be used for sealing hermetically alumina and niobium components in the construction of high pressure sodium lamps. Another application of the sealing materials described includes the formation of protective metal halide coatings on cermet materials and on a range of refractory metals such as niobium, tungsten, molybdenum, tantalum for the construction of ceramic metal halide discharge lamps containing sodium vapours and/or metal halide vapours.
The sealing materials of this invention can be used to join sintered alumina or artificial single crystal sapphire components, cermet components or alumina to cermet components of any convenient geometry for the construction of ceramic discharge lamps. Such lamps may show improved performance as regards efficiency, colour rendition and higher resistance to metal halide attack at elevated temperature than conventional metal halide lamps using silica envelopes.

Claims

1. A sealing composition for use in electrical discharge devices comprising by weight from 60 to 95% of a rare earth oxide, from 5 to 40% of boric oxide, an amount of up to 5% of phosphorus pentoxide, and an amount of up to 5% of one or of each of aluminium oxide and magnesium oxide.

2. A sealing composition according to claim 1 wherein the rare earth oxide comprises lanthanum oxide.

3. A sealing composition according to claim 1 or claim 2 comprising by weight from 60 to 95% of lanthanum oxide, from 5 to 40% of boric oxide and from 0 to 5% of the oxide of a rare earth other than lanthanum.

4. A sealing composition according to any one of claims 1 to 3 which comprises at least some of both aluminium oxide and magnesium oxide.

5. A sealing composition according to any one of claims 1 to 4 wherein the total amount of phosphorus pentoxide, aluminium oxide and/or magnesium oxide is up to 3% by weight.

6. A sealing composition according to any one of claims 1 to 5 wherein the rare earth oxide and boric oxide are present in substantially eutectic proportions.

7. A sealing composition according to claim 6 comprising by weight about 88% lanthanum oxide, 10.5% boric oxide, 0.5% aluminium oxide, 0.5% magnesium oxide and 0.5% phosphorus pentoxide.

8. A method of making a sealing compositions according to any one of claims 1 to 7 which comprises mixing together the appropriate quantities of the individual oxides or their salts, or in the case of phosphorus pentoxide a phosphate of one of the metals to be included, calcining the mixture and crushing the calcined material to a powder.

9. A method according to claim 8 wherein the mixture is fused to homogenize the materials before being calcined.

10. A method according to claim 9 wherein fusion is carried out at about 200°C and calcination at a temperature up to 1200°C.

11. A method according to any of claims 8 to 10 wherein the crushed material is made into a slurry with an organic liquid.

12. A method according to any of claims 8 to 10 wherein the crushed material is formed into a pressed element.

13. A method of making a seal in electric discharge devices, especially between ceramic and cermet components, which comprises applying a composition according to any of claims 1 to 7 to at least one of the surfaces to be joined, and bringing the surfaces into contact and heating them in a vacuum or inert atmosphere at 1100 to 1650°C.

14. An electric lamp or other discharge device incorporating a seal made by a method according to claim 13.